Composite anode active material, anode including the composite anode active material, lithium battery including the anode, and method of preparing the composite anode active material

ABSTRACT

A composite anode active material including metal core particles and carbon nanotubes that are covalently bound to the metal core particles, an anode including the composite anode active material, a lithium battery employing the anode, and a method of preparing the composite anode active material.

CROSS-REFERENCE TO RELATED APPLICATION

This application claims the benefit of Korean Patent Application No.10-2009-0007521, filed on Jan. 30, 2009, in the Korean IntellectualProperty Office, the disclosure of which is incorporated herein, byreference.

BACKGROUND

1. Field

One or more embodiments of the present teachings relate to a compositeanode active material, an anode including the composite anode activematerial, a lithium battery employing the anode, and a method ofpreparing the composite anode active material.

2. Description of the Related Art

Carbonaceous materials such as graphite are representative examples ofanode active materials for lithium batteries. Graphite has excellentelectrical capacity retention characteristics and excellent voltagecharacteristics. In addition, graphite does not vary in volume when usedto form an alloy with lithium, and thus, may increase the stability of abattery. Graphite has a theoretical electrical capacity of about 372mAh/g and a high irreversible capacity.

In addition, metals capable of forming alloys with lithium may be usedas an anode active material for lithium batteries. Examples of metalscapable of forming alloys with lithium include silicon (Si), tin (Sn),aluminum (Al), and the like. These metals have a very high electricalcapacity. For example, these metals may have an electrical capacity thatis 10 times higher than that of graphite. Such metals undergo a changein volume during charging and discharging, thereby electricallyisolating the active material within the electrode. In addition, anelectrolyte decomposition reaction becomes severe, due to an increase inspecific surface area of the active material. Si also has a relativelyhigh resistance.

Metals capable of forming alloys with lithium may be formed intocomposites with carbonaceous materials, in order to suppress volumetricexpansion and improve conductivity. However, conventional examples ofsuch composite materials rely only on Van der Waals forces for cohesion,and thus, the metal and the carbonaceous material are easily separatedduring charging and discharging. Thus, there is a demand for ahigh-capacity and long-lifespan active material for high-capacitylithium batteries.

SUMMARY

One or more embodiments of the present teachings include a compositeanode active material having a novel structure.

One or more embodiments of the present teachings include an anodeincluding the anode active material.

One or more embodiments of the present teachings include a lithiumbattery employing the anode.

One or more embodiments of the present teachings include a method ofpreparing the composite anode active material.

According to one or more embodiments of the present teachings, acomposite anode active material includes metal core particles; andcarbon nanotubes covalently bound to the metal core particles, so thatthe carbon nanotubes and the metal core particles are integrally formedas one body.

According to one or more embodiments of the present teachings, an anodeincludes the composite anode active material.

According to one or more embodiments of the present teachings, a lithiumbattery includes the anode.

According to one or more embodiments of the present teachings, a methodof preparing a composite anode active material includes: preparing amixed solution by mixing metal core particles, carbon nanotubes, and anorganic solvent; milling the mixed solution; drying the milled mixedsolution; and sintering the dried product in an inert gas atmosphere.

Additional aspects and/or advantages of the present teachings will beset forth in part in the description which follows and, in part, will beobvious from the description, or may be learned by practice of thepresent teachings.

BRIEF DESCRIPTION OF THE DRAWINGS

These and/or other aspects and advantages of the teachings will becomeapparent and more readily appreciated from the following description ofthe exemplary embodiments, taken in conjunction with the accompanyingdrawings, of which:

FIG. 1 illustrate X-ray photoelectric spectra of composite anode activematerials prepared according to Example 1 and Comparative Example 1;

FIG. 2 illustrates Raman spectra of the composite anode active materialsprepared according to Example 1, Comparative Example 1, and ReferenceExample 1; and

FIG. 3 illustrates a perspective view of a lithium secondary battery,according to aspects of the present disclosure.

DETAILED DESCRIPTION

Reference will now be made in detail to the exemplary embodiments of thepresent teachings, examples of which are illustrated in the accompanyingdrawings, wherein like reference numerals refer to the like elementsthroughout. The exemplary embodiments are described below, in order toexplain the aspects of the present teachings, by referring to thefigures.

One or more exemplary embodiments of the present teachings include acomposite anode active material including metal core particles andcarbon nanotubes covalently bound to the metal core particles, so thatthe carbon nanotubes and metal core particles are formed as a singlebody. Since the metal core particles and the carbon nanotubes are boundby covalent bonds, the metal core particles are not separated andisolated from the carbon nanotubes in a battery, even when the volume ofthe metal core particles varies during charging and discharging of thebattery. Thus, a lithium battery including the composite anode activematerial may have an increased capacity and retention rate. Thus, thelifespan thereof is increased. In addition, since the composite anodeactive material includes carbon nanotubes that have a high electricalconductivity, electrons migrate easily within the composite anode activematerial. Furthermore, in spite of the metal core particles having arelatively high resistance, a reduction in efficiency of the battery maybe prevented.

According to an exemplary embodiment, the metal core particles of thecomposite anode active material may include a metal capable of formingalloy with lithium. The metal may be any suitable metal that may be usedas an anode active material. These metals may include silicon (Si), tin(Sn), aluminum (Al), germanium (Ge), lead (Pb), bismuth (Bi), antimony(Sb), and alloys thereof. Alternatively, the metal core particles mayinclude a metal oxide capable of forming an alloy with lithium. In thisregard, the metal core particles may include a vanadium oxide, lithiumoxide, or the like.

According to an exemplary embodiment, the metal core particles may havean average particle diameter of 50 nm or less. For example, the metalcore particles may have an average particle diameter of from about 20 toabout 25 nm. If the metal core particles are non-spherical, the averageparticle diameter refers to the smallest diameter of a particle.

According to an exemplary embodiment, the carbon nanotubes may becrystalline carbon nanotubes. The carbon nanotubes may have a D/G valueof about 0.2 or less, which is a value obtained from the Raman spectrathereof and is obtained using Equation 1 below. For example, the carbonnanotubes may have a D/G value of from about 0.1 to about 0.15.D/G=Peak intensity of D band/Peak intensity of G band  <Equation 1>

If the D/G value is greater than about 0.2, the crystallinity of thecarbon nanotubes is relatively low, so that lithium ions are more liableto irreversibly react with the carbon nanotubes during charging anddischarging. Thus, the carbon nanotubes contribute to a lowerreversibility efficiency.

According to an exemplary embodiment, the amount of the carbon nanotubesin the composite anode active material may be in a range of from about2% to about 20% by weight, based on the total weight of the compositeanode active material.

According to an exemplary embodiment, the composite anode activematerial may not have a metal/carbon bulk phase, such as an SiC bulkphase. The absence of the metal/carbon bulk phase refers to thecomposite anode active material that includes substantially no othercarbonaceous material phase, except for carbon nanotubes (CNT).

According to an exemplary embodiment, the composite anode activematerial may further include oxygen. The amount of oxygen may be 25% byweight or less, based on the total weight of the composite anode activematerial. The amount of oxygen may be in a range of from about 1% toabout 25% by weight, based on the total weight of the composite anodeactive material.

According to an exemplary embodiment, the composite anode activematerial may further include a metal oxide capable of forming an alloywith lithium. The metal oxide may be represented by Formula 1, asfollows:MO_(y)  <Equation 1>

In Formula 1, M includes at least one metal selected from the groupconsisting of silicon (Si), aluminum (Al), germanium (Ge), lead (Pb),bismuth (Bi), tin (Sb), and alloys thereof, where 0.4≦y≦0.6. Forexample, the metal oxide may be SiO_(0.5).

One or more exemplary embodiments include an anode including thecomposite anode active material. For example, the anode may bemanufactured by molding an anode active material composition includingthe composite anode active material and a binder, into a desired shape,or coating the mixed anode material on a current collector, such ascopper foil, or the like.

In particular, the anode active material composition is prepared, andthen the mixed anode material composition may be directly coated on acopper foil current collector, to obtain an anode plate. Alternatively,the anode active material composition may be cast on a separate support,and then an anode active material film separated from the support islaminated on a copper foil current collector, to obtain an anode plate.The anode is not limited to the examples described above, and may be oneof a variety of types.

For high capacity batteries, it is necessary to charge and discharge alarge amount of current, and thus, a material having low electricalresistance may be used. Any suitable conducting agent that reduces theresistance of an electrode may be added to the anode. In this regard,the conducting agent may be carbon black, graphite particulates, or thelike. Alternatively, the anode active material composition may beprinted on a flexible electrode substrate, to manufacture a printablebattery.

FIG. 3 is a schematic perspective view of a lithium secondary battery30, according to an exemplary embodiment of the present teachings.Referring to FIG. 3, the lithium battery 30 includes a cathode plate 23,an anode plate 22, a separator 24 disposed between the cathode plate 23and the anode plate 22, an organic electrolyte solution (not shown), abattery container 25, and a sealing member 26 to seal the batterycontainer 25.

One or more exemplary embodiments include a lithium battery employingthe anode. The lithium battery may be manufactured in the followingmanner.

First, a cathode active material, a conducting agent, a binder, and asolvent are mixed to prepare a cathode active material composition. Thecathode active material composition is directly coated on a metalliccurrent collector and then dried, to prepare a cathode plate.Alternatively, the cathode active material composition may be cast on aseparate support, and then a cathode active material film separated fromthe support is laminated on a metallic current collector, to prepare acathode plate.

Any lithium-containing metal oxide that is commonly used in the art maybe used as the cathode active material. Examples of thelithium-containing metal oxide include LiCoO₂, LiMn_(x)O_(2x) where x=1or 2, LiNi_(1-x)Mn_(x)O₂ where 0<x<1, or LiNi_(1−x−y)Co_(x)Mn_(y)O₂where 0≦x≦0.5 and 0≦y≦0.5. Specific examples of the lithium-containingmetal oxide include compounds capable of the intercalation anddeintercalation of lithium ions, such as, LiMn₂O₄, LiCoO₂, LiNiO₂,LiFeO₂, V₂O₅, TiS, MoS, or the like. The conducting agent may includecarbon black or a graphite particulate. Examples of the binder include avinylidene fluoride/hexafluoropropylene copolymer, polyvinylidenefluoride (PVDF), polyacrylonitrile, polymethylmethacrylate,polytetrafluoroethylene, mixtures of these materials, and a styrenebutadiene rubber polymer. The solvent may include N-methyl-pyrrolidone,acetone, water, or the like. Here, the amounts of the cathode electrodeactive material, the conducting agent, the binder, and the solvent areamounts generally used in the art.

A separator used in the lithium battery may be any separator that iscommonly used for lithium batteries. The separator may have lowresistance to the migration of ions in an electrolyte and may have anexcellent electrolyte-retaining ability. Examples of the separator mayinclude glass fiber, polyester, polyethylene, polypropylene, afluoropolymer such as polytetrafluoroethylene (PTFE), and a combinationthereof. The separator may be in non-woven or woven fabric form. Inparticular, a woundable separator including polyethylene, polypropylene,or the like, may be used. A separator that retains a large amount of anorganic electrolytic solution may be used. The separator may bemanufactured using the following method.

A polymer resin, a filler, and a solvent are mixed to prepare aseparator composition. The separator composition is directly coated onan electrode and then dried, to form a separator film. Alternately, theseparator composition may be cast onto a separate support, dried,detached from the separate support, and then finally laminated on anupper portion of the electrode, thereby forming a separator film.

The polymer resin may be any polymer resin that is commonly used forbinding electrode plates in lithium batteries. Examples of the polymerresin may include a vinylidenefluoride/hexafluoropropylene copolymer,polyvinylidene fluoride (PVDF), polyacrylonitrile,polymethylmethacrylate, and a mixture thereof.

An electrolytic solution used in the lithium battery is prepared bydissolving an electrolyte in a solvent. The solvent may be selected fromthe group consisting of propylene carbonate, ethylene carbonate,fluoroethylene carbonate, diethyl carbonate, methylethyl carbonate,methylpropyl carbonate, butylene carbonate, benzonitrile, acetonitrile,tetrahydrofuran, 2-methyltetrahydrofuran, γ-butyrolactone, dioxorane,4-methyldioxorane, N,N-dimethyl formamide, dimethyl acetamide,dimethylsulfoxide, dioxane, 1,2-dimethoxyethane, sulforane,dichloroethane, chlorobenzene, nitrobenzene, dimethyl carbonate,methylisopropyl carbonate, ethylpropyl carbonate, dipropyl carbonate,dibutyl carbonate, diethylene glycol, dimethyl ether, and mixturesthereof. The electrolyte may be a lithium salt, such as LiPF₆, LiBF₄,LiSbF₆, LiAsF₆, LiClO₄, LiCF₃SO₃, Li(CF₃SO₂)₂N, LiC₄F₉SO₃, LiAlO₂,LiAlCl₄, LiN(C_(x)F_(2x+1)SO₂)(C_(y)F_(2y+1)SO₂) where x and y are eachindependently a natural number, LiCl, LiI, or mixtures thereof.

The separator 24 is interposed between the cathode plate 23 and theanode plate 22, and the resultant is wound or folded to form anelectrode assembly. The electrode assembly is encased in the batterycontainer 25. The battery container 25 is shown as being cylindrical,but may also be rectangular in some aspects. The organic electrolytesolution is then injected into the battery container 25, thereby formingthe lithium ion battery 30.

Alternatively, the electrode assembly is formed as a laminated bi-cellstructure, which is impregnated with the organic electrolytic solution.The electrode assembly is put into a pouch, which is then sealed,thereby forming a lithium ion polymer battery.

One or more exemplary embodiments of the present teachings include amethod of preparing a composite anode active material, the methodincluding: preparing a mixed solution, by mixing metal core particles,carbon nanotubes, and an organic solvent; milling the mixed solution;drying the milled mixed solution; and sintering the dried product in aninert gas atmosphere.

The mixed solution is prepared by mixing metal core particles, carbonnanotubes, and an organic solvent. The mixed solution is milled using amiller, at a rotation rate of from about 50 to about 55 Hz, for fromabout 1 to about 2 hours, followed by drying the resultant product.Next, the dried product is sintered at a temperature of from about 700to about 1400° C., for from about 1 to 4 hours, thereby obtaining thecomposite anode active material. The metal core particles and the carbonnanotubes form a composite during the milling process. Covalent bondsare formed between the metal core particles and the carbon nanotubes,during the sintering process. The mill used for the milling process maybe a bead mill, a high-energy milling apparatus, or the like.

According to an exemplary embodiment, the amount of the carbon nanotubesin the mixed solution may be in a range of from about 2% to about 20% byweight, based on the total weight of the metal core particles and thecarbon nanotubes.

According to an exemplary embodiment, the amount of oxygen in theorganic solvent molecule may be about 25% by weight or less, based onthe total molecular weight of the organic solvent molecule. For example,the organic solvent may include a C4-C20, straight or branched, alcohol.In this regard, the organic solvent may include butanol, octanol, or thelike.

According to an exemplary embodiment, the sintering process may beperformed at a temperature of from about 600° C. to about 1400° C. Forexample, sintering process may be performed at a temperature of fromabout 600° C. to about 900° C.

Hereinafter, one or more embodiments of the present teachings will bedescribed in detail, with reference to the following examples. However,these examples are not intended to limit the scope of the presentteachings.

Preparation of Anode Active Material

Example 1

Silicon (Si) powder (High Purity Chemicals Co., Japan) having an averageparticle diameter of 4 nm and carbon nanotubes (CVD-SWCNT 601 CE, CarbonNanotechnologies Inc., USA) were mixed at a weight ratio of 9:1. 6 g ofthe mixture was added to 200 ml of 1-octanol constituting a solvent, toprepare a mixed solution. The mixed solution was placed in a bead mill(Ultra Apex Mill UAM-015, Kotobuki Ind. Co.) and milled at a rotationrate of 55 Hz, at room temperature, for 2 hours. The solvent of themilled mixed solution was evaporated in an oven, at a temperature of 80°C., and then thermally treated at 800° C. in a nitrogen atmosphere, for2 hours, thereby obtaining a composite anode active material.

Comparative Example 1

Silicon (Si) powder (High Purity Chemicals Co., Japan) having an averageparticle diameter of 4 nm and carbon nanotubes (CVD-SWCNT 601 CE, CarbonNanotechnologies Inc., USA) were mixed at a weight ratio of 9:1. 6 g ofthe mixture was added to 200 ml of 1-octanol, constituting a solvent, toprepare a mixed solution. The mixed solution was placed in a bead mill(Ultra Apex Mill UAM-015, Kotobuki Ind. Co.) and milled at a rotationrate of 55 Hz, at room temperature, for 2 hours. Next, the solvent ofthe milled mixed solution was evaporated in an oven, at temperature of80° C.

Comparative Example 2

A composite anode active material was prepared in the same manner as inComparative Example 1, except that the milling time was 1 hour.

Comparative Example 3

A composite anode active material was prepared in the same manner as inComparative Example 1, except that ethanol was used as the organicsolvent, and the milling time was 1 hour.

Reference Example 1

Carbon nanotubes (CVD-SWCNT 6010E, Carbon Nanotechnologies Inc., USA)were used as received for Raman spectroscopy.

Manufacture of Anode and Lithium Battery

Example 2

55% by weight of the composite anode active material, in powder form,prepared in Example 1 and 30% by weight of a carbonaceous conductingagent (SFG6, Timcal Inc.), in dried form, were mixed in an agate mortar,and then mixed with 15% by weight of a 5 wt % polyvinylidene fluoride(PVDF) solution, in N-methylpyrrolidone, to obtain a slurry. The slurrywas coated on a Cu current collector using a doctor blade, to athickness of 100 μm, dried at 90° C. for 1 hour, and then dried again at120° C. in a vacuum, for 2 hours. Next, the dried slurry was subjectedto a rolling process until the thickness of the dried slurry, initiallydeposited to a thickness of 50 nm, reached 30 nm, thereby obtaining ananode plate.

The anode plate, a lithium metal constituting a counter electrode, apolypropylene layer (Cellgard 3510) constituting a separator, and anelectrolyte solution obtained by dissolving 1.3 M of LiPF₆ in a mixedsolvent of ethylene carbonate (EC) and diethylene carbonate (DEC)(volume ratio of 3:7) were used to manufacture a CR-2016 standard coincell.

Comparative Examples 4 Through 6

Lithium batteries were manufactured in the same manner as in Example 2,except that the anode active materials of Comparative Examples 1, 2, and3 were used instead of the composite anode active material of Example 1.

Evaluation Example 1 XPS (X-Ray Photoelectron Spectroscopy) Analysis

XPS analysis was performed on the composite anode active materialpowders prepared in Example 1 and Comparative Example 1. The results areshown in FIG. 1. As can be seen in FIG. 1, a shoulder corresponding toSi—C covalent bonds was identified near 282.4 eV, in the XPS spectra ofthe composite anode active material of Example 1. However, for thecomposite anode active material of Comparative Example 1, no shoulderappeared.

Evaluation Example 2 Measurement of Raman Spectrum

Raman spectrum analysis was performed on the composite anode activematerial powders of Example 1 and Comparative Example 1, and the carbonnanotubes of Reference Example 1, and the results are shown in FIG. 2and Table 1 below.

TABLE 1 D/G Example 1 0.15 Comparative Example 1 0.30 Reference Example1 0.15

As shown in Table 1, the composite anode active material of Example 1had a smaller D/G value, which was obtained using Equation 1 below, thanthe composite anode active material of Comparative Example 1. The D/Gvalue of the composite anode active material of Example 1 corresponds tothe D/G value of the pure carbon nanotubes of Reference Example 1.Therefore, it can be confirmed that, in comparison to the compositeanode active material of Comparative Example 1, which includes amorphouscarbon, the composite anode active material of Example 1 includes anegligible amount of amorphous carbon.D/G=Peak intensity of D band/Peak intensity of G band  <Equation 1>

Evaluation Example 3 X-Ray Diffraction Test

An X-ray diffraction test was performed on the composite anode activematerials prepared in Example 1 and Comparative Examples 1, 2 and 3, atλ=1.54184 Å, in order to measure full maximum at half width (FMHW) and θvalues. Then, the particle size of Si was calculated from the FMHW and θvalues, using Scherrer's equation (Equation 2 below). The results areshown in Table 2 below. The two particle diameters in Table 2 for eachof the composite anode active materials of Example 1 and ComparativeExamples 1, 2, and 3 were calculated from two 2θ values respectivelymeasured on the planes (111) and (220), which denote Miller indices(hkl).Particle diameter=λ/[FWHM×cos θ]  <Equation 2>

TABLE 2 FWHM 2θ Particle diameter (nm) Example 1 0.3928 28.44176 23.20.4674 47.33073 20.6 Comparative Example 1 0.4157 28.46004 21.9 0.460547.35474 20.9 Comparative Example 2 0.3132 28.49615 29.1 0.3697 47.3803026.1 Comparative Example 3 0.6305 28.43590 14.5 0.6789 47.33582 14.2

As can be seen in Table 2, for the composite anode active material ofExample 1, the Si metal core particles had a particle diameter of fromabout 20 to about 25 nm.

Evaluation Example 4 Composition Analysis

The amounts of elements constituting the composite anode active materialof Example 1 were analyzed using an ion coupled plasma (ICP) analyzer(ICP-AES on Shimadzu ICPS-8100 sequential spectrometer) and a CNS(carbon/nitrogen/sulfur) analyzer (Flash EA 1112, Thermo Electroncorporation, USA). The percentage of oxygen was calculated bysubtracting the proportions of the elements from 100%. The results areshown in Table 3 below.

TABLE 3 Example 1 Si O C N H Amount [wt %] 69.1 21.1 9.4 0.3 0.1

The amount of oxygen in the composite anode active material was lessthan 25%. Considering the amount of oxygen in the composite anode activematerial on a mole basis, the silicon oxide can be represented bySiO_(0.54).

Evaluation Example 5 Charge-Discharge Test

The lithium batteries manufactured according to Example 2 andComparative Examples 4 through 6 were charged until the voltage thereofreached 0.0V (with respect to the Li metal), by a current of 100 mA per1 g of the composite anode active material, and then discharged at thesame rate, until the voltage reached 1.5V (with respect to the Limetal). Then, the cycle of charging and discharging was repeated 12times. The results are shown in Table 4 below. An initial dischargecapacity refers to a discharge capacity at the 1^(st) cycle. An initialcoulombic efficiency refers to a ratio of discharge capacity to chargecapacity at the 1^(st) cycle (Coulombic efficiency=Dischargecapacity/Charge capacity). A capacity retention rate at the 10^(th)cycle refers to a ratio of the discharge capacity at the 10^(th) cycleto the discharge capacity at the 1^(st) cycle (Capacity retention rateat the 10^(th) cycle=Discharge capacity at the 10^(th) cycle/Dischargecapacity at the 1^(st) cycle).

TABLE 4 Initial Capacity discharge Initial retention capacity coulombicrate at [mAh/g] efficiency [%] 10^(th) cycle [%] Example 2 1439 78.5 93Comparative Example 4 1073 62.6 15 Comparative Example 5 1308 69.5 15Comparative Example 6 910 69.8 81

As can be seen in Table 4, the lithium battery of Example 2 had amarkedly improved lifespan (capacity retention rate), as compared to thelithium batteries of Comparative Examples 4 and 5, and had a markedlyincreased initial discharging capacity, as compared to the lithiumbattery of Comparative Example 6. In addition, for the lithium batteryof Example 2, the capacity density was maintained at 1000 mAh/g orgreater, indicating a remarkable improvement over lithium batteriesincluding only carbonaceous anode active materials.

As described above, according to the one or more of the above exemplaryembodiments, a lithium battery including a composite anode activematerial that includes carbon nanotubes covalently bound to metal coreparticles has an excellent capacity retention rate.

Although a few exemplary embodiments of the present teachings have beenshown and described, it would be appreciated by those skilled in the artthat changes may be made in these exemplary embodiments, withoutdeparting from the principles and spirit of the present teachings, thescope of which is defined in the claims and their equivalents.

What is claimed is:
 1. A composite anode active material comprising amixture of: metal core particles; and carbon nanotubes that arecovalently bound to the metal core particles, wherein the compositeanode active material is free of a carbonaceous material except for thecarbon nanotubes.
 2. The composite anode active material of claim 1,wherein the metal core particles comprise a metal capable of forming analloy with lithium.
 3. The composite anode active material of claim 1,wherein the metal core particles comprise at least one metal selectedfrom the group consisting of silicon (Si), aluminum (Al), germanium(Ge), lead (Pb), bismuth (Bi), tin (Sn), and an alloy thereof.
 4. Thecomposite anode active material of claim 1, wherein the metal coreparticles have a diameter of less than about 50 nm.
 5. The compositeanode active material of claim 1, wherein the carbon nanotubes comprisecrystalline carbon nanotubes.
 6. The composite anode active material ofclaim 1, wherein the carbon nanotubes have a D/G value of less thanabout 0.2, obtained from Raman spectra using Equation 1:D/G=Peak intensity of D band/Peak intensity of G band.  Equation 1 7.The composite anode active material of claim 1, wherein the amount ofthe carbon nanotubes is from about 2% to about 20% by weight, based onthe total weight of the composite anode active material.
 8. Thecomposite anode active material of claim 1, further comprising oxygen.9. The composite anode active material of claim 8, wherein the amount ofoxygen is less than about 25% by weight, based on the total weight ofthe composite anode active material.
 10. The composite anode activematerial of claim 1, further comprising a metal oxide capable of formingan alloy with lithium.
 11. The composite anode active material of claim10, wherein the metal oxide is represented by Formula 1:MO_(y),  <Formula 1> wherein M comprises at least one metal selectedfrom the group consisting of silicon (Si), aluminum (Al), germanium(Ge), lead (Pb), bismuth (Bi), tin (Sb), and an alloy thereof, and0.4≦y≦0.6.
 12. An anode comprising the composite anode active materialof claim
 1. 13. A lithium battery comprising the anode of claim 12.